Semiconductor device and method of manufacturing the same

ABSTRACT

There is provided a semiconductor device which comprises a first interlayer insulating film (first insulating film) formed over a silicon (semiconductor) substrate, a capacitor formed on the first interlayer insulating film and having a lower electrode, a dielectric film, and an upper electrode, a fourth interlayer insulating film (second insulating film) formed over the capacitor and the first interlayer insulating film, and a metal pattern formed on the fourth interlayer insulating film over the capacitor and its periphery to have a stress in an opposite direction to the fourth interlayer insulating film. As a result, characteristics of the capacitor covered with the interlayer insulating film can be improved.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims priority of Japanese PatentApplication No. 2002-255036, filed on Aug. 30, 2002, the contents beingincorporated herein by reference.

BACKGOUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a semiconductor device and a method ofmanufacturing the same and, more particularly, to a semiconductor devicehaving a capacitor and a method of manufacturing the same.

2. Description of the Related Art

As the nonvolatile memory that can stores the information after thepower supply is turned OFF, the flash memory and the ferroelectricmemory (FeRAM) are known.

The flash memory has the floating gate buried in the gate insulatingfilm of the insulated gate field effect transistor (IGFET), and storesthe information by accumulating the charge, as the stored information,in the floating gate. In order to write and erase the information,tunnel current must be supplied to the gate insulating film, whichrequires a relatively high voltage.

The FeRAM has the ferroelectric capacitor that stores the information byutilizing the hysteresis characteristic of the ferroelectric substance.The ferroelectric film formed between the upper electrode and the lowerelectrode in the ferroelectric capacitor causes the polarization inresponse to the value of the voltage applied between the upper and lowerelectrodes, thereby leaving the spontaneous polarization after theapplied voltage is removed. When the polarity of the applied voltage isreversed, the polarity of the spontaneous polarization is also reversed.The information can be read by detecting the polarity and the magnitudeof this spontaneous polarization.

The FeRAM has an advantage in that it operates with lower voltage andhigher writing speed at lower power consumption than the flash memory.

As set forth in Patent Application Publication (KOKAI) 2001-60669, forexample, the memory cell of the FeRAM has the MOS transistor formed onthe silicon substrate, the first interlayer insulating film formed onthe silicon substrate and the MOS transistor, the ferroelectriccapacitor formed on the first interlayer insulating film, the secondinterlayer insulating film formed on the ferroelectric capacitor and thefirst interlayer insulating film, the conductive plug buried in the holethat is formed in the first and second interlayer insulating films andconnected to the MOS transistor, the first wiring pattern for connectingthe conductive plug and the upper electrode of the ferroelectriccapacitor, the third interlayer insulating film formed on the firstwiring pattern and the second interlayer insulating film, and the secondwiring pattern formed on the third interlayer insulating film.

The interlayer insulating film for covering the ferroelectric capacitorhas a strong compressive stress, which generates a force in thedirection that the insulating film itself expands. As a result, ashrinkage force is applied to the ferroelectric capacitor every timewhen the interlayer insulating films are formed on the ferroelectriccapacitor to overlap with each other, which causes the degradation ofthe characteristics of the ferroelectric capacitor.

Also, when the first wiring pattern is formed of aluminum, the residualpolarization characteristic of the ferroelectric capacitor degrades dueto a tensile force of the first wiring pattern. In contrast, in PatentApplication Publication (KOKAI) 2001-36025, it is set forth that thealuminum film is heated at the temperature exceeding a Curie point ofthe ferroelectric film of the ferroelectric capacitor for the purpose ofrelaxing the tensile force and, after that, the wiring pattern is formedby patterning the aluminum film.

However, since there exists the interlayer insulating film in the gapsbetween the first wiring pattern, there remains problem that thecompressive stress of the interlayer insulating film degrades theferroelectric capacitor, irrespective of the stress of the first wringpattern.

In contrast, in Patent Application Publication (KOKAI) Hei 11-330390, itis set forth that the interlayer insulating film is formed to have thetensile stress to the ferroelectric capacitor. However, the interlayerinsulating film having the tensile stress contains a large amount ofmoisture, which poses another problem that moisture degrades thecapacitor.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a semiconductordevice capable of improving characteristics of a capacitor that iscovered with an interlayer insulating film, and a method ofmanufacturing the same.

According to an aspect of the present invention, there is provided asemiconductor device which comprises a first insulating film formed overa semiconductor substrate; a capacitor formed on the first insulatingfilm and having a lower electrode, a dielectric film, and an upperelectrode; a second insulating film formed over the capacitor and thefirst insulating film; and a metal pattern formed on the secondinsulating film over the capacitor and a periphery thereof and having astress in an opposite direction to a stress of the second insulatingfilm.

Next, an advantage of the present invention will be explained hereunder.

According to the semiconductor device of the present invention, themetal pattern having the stress in the opposite direction to the stressof the second insulating film is provided. Therefore, the stress appliedfrom the second insulating film to the capacitor can be relaxed by thestress of the metal pattern and thus the ferroelectric characteristic ofthe capacitor can be improved. In addition, since the metal pattern doesnot discharge the moisture unlike the insulating film, the capacitor isnot deteriorated by the moisture.

Such metal pattern may be formed on the second insulating film or may beformed in the recess that is formed in the second insulating film.

According to another aspect of the present invention, there is provideda manufacturing method of semiconductor device which comprises the stepsof forming a first insulating film over a semiconductor substrate;forming capacitors, each having a lower electrode, a dielectric film,and an upper electrode, on the first insulating film in a cell region;forming a second insulating film over the capacitor and the firstinsulating film; forming a metal film on the second insulating film;forming a metal pattern, which covers the cell region, by patterning themetal film; and heating the metal film at a melting point or less of themetal film before or after the formation of the metal pattern, to changea stress of the metal film.

Next, another advantage of the present invention will be explainedhereunder.

According to the manufacturing method of semiconductor device of thepresent invention, the stress of the metal film is changed by heatingthe metal film at the temperature of the melting point or less before orafter the formation of the metal pattern. Therefore, for example, if thestress of the metal film is changed into the opposite stress to thestress of the second insulating film, the stress of the secondinsulating film can be relaxed by the metal film and thus theferroelectric characteristic of the capacitor can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1, FIG. 2, FIG. 3, FIG. 4, FIG. 5, FIG. 6, FIG. 7, FIG. 8, FIG. 9,FIG. 10, FIG. 11, FIG. 12, and FIG. 13 are sectional views showing stepsof forming a semiconductor device according to a first embodiment of thepresent invention;

FIG. 14 is a plan view showing the semiconductor device according to thefirst embodiment of the present invention;

FIG. 15 is a view showing yield of FeRAM according to the firstembodiment of the present invention and yield of FeRAM formed in theprior art;

FIG. 16 is a view showing the characteristic of the ferroelectriccapacitor in the FeRAM according to the first embodiment of the presentinvention and the characteristic of the ferroelectric capacitor in theFeRAM formed in the prior art;

FIG. 17 is a view showing change in the stress by the annealing of themetal film;

FIGS. 18A to 18C, FIGS. 19A to 19C, FIGS. 20A to 20C, FIGS. 21A and 21B,FIGS. 22A and 22B, FIGS. 23A and 23B, FIGS. 24A and 24B, FIGS. 25A and25B, FIGS. 26A and 26B, FIG. 27, FIG. 28, FIG. 29, FIG. 30, FIG. 31, andFIG. 32 are sectional views showing steps of forming a semiconductordevice according to a second embodiment of the present invention; and

FIG. 33 is view showing a configuration of a copper film formingequipment employed in the steps of forming the semiconductor deviceaccording to the second embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Embodiments of the present invention will be explained with reference tothe drawings hereinafter.

First Embodiment

FIGS. 1 to 13 are sectional views showing a method of manufacturingsemiconductor device according to a first embodiment of the presentinvention in order of step. FIG. 14 is a plan view showing thesemiconductor device in FIG. 13.

First, steps for forming the structure shown in FIG. 1 will beexplained.

As shown in FIG. 1, LOCOS (Local Oxidation of Silicon) is formed as anelement isolation insulating film 2 on a part of a surface of a p-typesilicon (semiconductor) substrate 1. Another element isolation structuremay be employed in place of the insulating film 2, such as STI (ShallowTrench Isolation).

After the element isolation insulating film 2 is formed, a p-well 3 andan n-well 4 are formed by selectively introducing the p-type impurityand the n-type impurity into the predetermined active regions in amemory cell region A and a peripheral circuit region B of the siliconsubstrate 1. It should be noted that p-well is also formed in theperipheral circuit regions for forming CMOS, although not shown FIG. 1.

Then, silicon oxide films are formed as a gate insulating film 5 bythermally oxidizing the surfaces of the active regions of the siliconsubstrate 1.

Then, an amorphous silicon film and a tungsten silicide film are formedon the overall upper surface of the silicon substrate 1. Then, gateelectrodes 6 a, 6 b, 6 c and a wiring 7 are formed by patterning theamorphous silicon film and the tungsten silicide film into predeterminedshapes by virtue of the photolithography method. In this case, apolysilicon film may be formed in place of the amorphous silicon film.

In the memory cell region A, two gate electrodes 6 a, 6 b are arrangedin almost parallel on one p-well 3, and these gate electrodes 6 a, 6 bconstitute a part of the word line WL.

Then, the n-type impurity is ion-implanted into the p-well 3 in thememory cell region A on both sides of the gate electrodes 6 a, 6 b.Thus, n-type impurity diffusion regions 8 a, 8 b serving as thesource/drain of the n-channel MOS transistor are formed. At the sametime, an n-type impurity diffusion region may be formed in the p-well(not shown) in the peripheral circuit region B. Then, the p-typeimpurity is ion-implanted into the n-well 4 in the peripheral circuitregion B on both sides of the gate electrode 6 c. Thus, p-type impuritydiffusion regions 9 serving as the source/drain of the p-channel MOStransistor are formed. The individual implantation of the n-typeimpurity and the p-type impurity is carried out by using a resistpattern respectively.

Then, an insulating film is formed on an overall surface of the siliconsubstrate 1. Then, sidewalls 10 are left only on both side portions ofthe gate electrodes 6 a, 6 b, 6 c and the wiring 7 by etching back theinsulating film. As the insulating film, a silicon oxide (SiO₂) film isformed by the CVD method, for example.

Then, a silicon oxide nitride (SiON) film of about 200 nm thickness isformed as a cover film on the overall surface of the silicon substrate 1by the plasma CVD method. Then, a silicon oxide (SiO₂) film of about 1.0μm thickness is grown on the cover film by the plasma CVD method using aTEOS gas. A first interlayer insulating film (first insulating film) 11is constructed by the SiON film and the SiO₂ film. It should beunderstood that the SiO₂ film formed by the plasma CVD method using theTEOS gas is also referred to as TEOS film hereinafter.

Then, as the densifying process of the first interlayer insulating film11, the first interlayer insulating film 11 is annealed at thetemperature of 700° C. for 30 minutes in the atmospheric-pressurenitrogen atmosphere. Thereafter, the upper surface of the firstinterlayer insulating film 11 is planarized by polishing the firstinterlayer insulating film 11 by virtue of the chemical mechanicalpolishing (abbreviated as “CMP” hereinafter) method.

Then, contact holes 11 a to 11 d having depths, which reach the n-typeimpurity diffusion regions 8 a, 8 b on both sides of the gate electrodes6 a, 6 b in the memory cell region A and the p-type impurity diffusionregions 9 in the peripheral circuit region B respectively, and a viahole 11 e having a depth, which reaches the wiring 7 in the peripheralcircuit region B, are formed in the first interlayer insulating film 11by the photolithography method respectively. Then, a Ti (titanium) thinfilm of 20 nm thickness and a TiN (titanium nitride) thin film of 50 nmthickness are formed sequentially on an upper surface of the firstinterlayer insulating film 11 and the inner surfaces of the holes 11 ato 11 f by the sputter method. Then, a W (tungsten) film is grown on theTiN thin film by the CVD method. As a result, the tungsten film isburied in the contact holes 11 a to 11 d and the via hole 11 e.

Then, the W film, the TiN thin film, and the Ti thin film are polishedby the CMP method until an upper surface of the first interlayerinsulating film 11 is exposed. The tungsten film, etc., which are leftin the holes 11 a to 11 e after the polishing, are used as conductiveplugs 13 a to 13 e that electrically connect wirings described later andthe impurity diffusion regions 8 a, 8 b, 9 and the wiring 7.

In one p-well 3 in the memory cell region A, the first conductive plug13 a that is formed on the n-type impurity diffusion region 8 a beingput between two gate electrodes 6 a, 6 b is connected to the bit linedescribed later. Also, the second conductive plugs 13 b that are formedon both sides of the first conductive plug 13 a are connected to thecapacitors described later.

Then, in order to prevent the oxidation of the conductive plugs 13 a to13 e, an SiON film 14 of 100 nm thickness is formed on the firstinterlayer insulating film 11 and the conductive plugs 13 a to 13 e bythe plasma CVD method. Then, an SiO₂ film 15 of 150 nm thickness isformed by using TEOS as the film forming gas. Then, the SiON film 14 andthe SiO₂ film 15 are annealed at the temperature of 650 to 700° C. todegas the gas from these films.

Next, steps for forming the structure shown in FIG. 2 will be explainedhereunder.

First, a first conductive film 16 having a double-layered structure isformed by depositing a Ti layer and a Pt layer on the SiO₂ film 15sequentially by the DC sputter method to have a thickness of 20 nm and athickness of 175 nm respectively.

Then, a lead zirconate titanate (Pb(Zr_(1-x)Ti_(x))O₃; PZT) film as theferroelectric material is formed on the first conductive film 16 by theRF sputter method to have a thickness of 100 to 300 nm, e.g., 200 nm.Thus, a PZT film 17 is formed.

As the method of forming the ferroelectric material film, there are thespin-on method, the sol-gel method, the MOD (Metal Organic Deposition)method, the MOCVD method, etc. in addition to the above sputter method.Also, as the ferroelectric material, there are lead lanthanum zirconatetitanate (PLZT), SrBi₂(Ta_(x)Nb_(1-x))₂O₉ (where 0<x<1), Bi₄Ti₂O₁₂, etc.in addition to PZT. Furthermore, if DRAM is to be formed, thehigh-dielectric material such as (BaSr)TiO₃ (BST), strontium titanate(STO), etc. may be employed in place of the above ferroelectricmaterial.

Then, as the crystallizing process of the PZT film 17, RTA (RapidThermal Annealing) is executed at the temperature of 75° C. for 60second in the oxygen atmosphere.

Then, an IrO_(x) film of about 200 nm thickness is formed as a secondconductive film 18 on the PZT film 17 by the DC sputter method.

Next, steps for forming the structure shown in FIG. 3 will be explainedhereunder.

First, upper electrodes 18 a are formed by patterning the secondconductive film 18. Then, in order to remove the damage of the PZT film17 which is the ferroelectric substance, the recovery annealing of thePZT film 17 is executed at 650° C. for 60 minute in the oxygenatmosphere, for example.

Then, capacitor dielectric films 17 a are left at least under the upperelectrodes 18 a by patterning the PZT film 17. Then, the dielectricfilms 17 a are annealed at 650° C. for 60 minute in the oxygenatmosphere, for example.

Then, as shown in FIG. 4, first capacitor protection insulating films 19made of aluminum oxide (Al₂O₃) are formed on the upper electrodes 18 a,the dielectric films 17 a, and the first conductive film 16 by thesputter to have a thickness of 50 nm. Then, in order to relax the damageof the dielectric films 17 a caused by the sputter, the dielectric films17 a are annealed at 550° C. for 60 minute in the oxygen atmosphere, forexample.

Then, as shown in FIG. 5, lower electrodes 16 a are formed by patterningthe first conductive film 16. The first capacitor protection insulatingfilms 19 is patterned, along with the first conductive film 16.

Thus, ferroelectric capacitors 20 each consisting of the upper electrode18 a, the dielectric film 17 a, and the lower electrode 16 a are formed.Then, the ferroelectric capacitors 20 are annealed at 650° C. for 30minute in the oxygen atmosphere, for example.

Next, steps for forming the structure shown in FIG. 6 will be explainedhereunder.

First, a second interlayer insulating film 21 is formed on theferroelectric capacitors 20 and the overall surface of the SiO₂ film 15.The second interlayer insulating film 21 is formed as a double-layeredstructure that consists of an insulating film, which is formed first byusing TEOS to have a thickness of about 480 nm, and an SOG film, whichis formed on the insulating film to have a thickness of about 90 nm.Then, a thickness of the second interlayer insulating film 21 is reducedto about 270 nm by etching back these films by a thickness of about 300nm.

Then, the plasma annealing is applied to the second interlayerinsulating film 21 and various films thereunder at the temperature of350° C. by using the N₂O gas. In this plasma annealing, the siliconsubstrate 1 is loaded into the chamber of the plasma generatingequipment, then an N₂O gas and an N₂ gas are introduced into the chamberat flow rates of 700 sccm and 200 sccm respectively, and then the secondinterlayer insulating film 21 and various underlying films are exposedto the plasma at the substrate temperature of less than 450° C. for thetime of more than 1 minute. As a result, the nitrogen is caused to comedeeply into the inside from a surface of the second interlayerinsulating film 21 to prevent the penetration of the moisture. In thefollowing, this process is called the N₂O plasma process. In thisembodiment, 350° C. and 2 minutes, for example, are selected as theannealing temperature and the annealing time respectively.

Next, steps for forming the structure shown in FIG. 7 will be explainedhereunder.

First, first contact holes 21 a are formed in the second interlayerinsulating film 21 on the upper electrodes 16 a of the ferroelectriccapacitors 20 by the photolithography method. At the same time, contactholes (not shown) are formed on the contact areas of the lowerelectrodes, which are arranged in the direction perpendicular to thissheet of FIG. 7. Then, the recovery annealing is applied to thedielectric films 17 a. Specifically, the dielectric films 17 a areannealed at the temperature of 550° C. for 60 minute in the oxygenatmosphere.

Then, the second interlayer insulating film 21, the SiO₂ film 15, andthe SiON film 14 are patterned by the photolithography method. Thus,second contact holes 21 b are formed on the second conductive plugs 13b, which are located near both ends of the p-well 3 in the memory cellregion A, respectively to expose the second conductive plugs 13 b. Then,a TiN film of 125 nm thickness is formed on the second interlayerinsulating film 21 and in the contact holes 21 a, 21 b by the sputtermethod. Then, the TiN film is patterned by the photolithography method.Thus, local wirings 22 a each of which electrically connects the secondconductive plug 13 b and the upper electrode 18 a of the ferroelectriccapacitor 20 via the contact holes 21 a, 21 b in the memory cell regionA are formed. Then, the annealing is applied to the second interlayerinsulating film 21 at 350° C. for 30 minute in the nitrogen (N₂)atmosphere.

Then, a second capacitor protection insulating film 23 made of aluminumoxide is formed on the local wirings 22 a and the second interlayerinsulating film 21 by the sputter method to have a thickness of 20 nm.

Then, a silicon oxide film of about 300 nm thickness is formed as athird interlayer insulating film 24 on the local wirings 22 a and thesecond interlayer insulating film 21 by the plasma CVD method using theTEOS gas. Then, the reforming of the third interlayer insulating film 24is executed by the N₂O plasma process. The conditions of the N₂O plasmaprocess are set to the same conditions as the N₂O plasma process appliedto the second interlayer insulating film 21.

Next, steps for forming the structure shown in FIG. 8 will be explainedhereunder.

First, each films ranging from the third interlayer insulating film 24to the SiON film 14 in the memory cell region A are patterned by thephotolithography method. Thus, a contact hole 24 a is formed on thefirst conductive plug 13 a positioned in the center of the p-well 3. Atthe same time, contact holes 24 c to 24 e are formed on the conductiveplugs 13 c to 13 e in the peripheral circuit region B.

Then, five layers consisting of a Ti film of 20 nm thickness, a TiN filmof 50 nm thickness, an Al—Cu film of 600 nm thickness, a Ti film of 5 nmthickness, and a TiN film of 150 nm thickness are laminated sequentiallyon the third interlayer insulating film 24 and in the contact holes 24 cto 24 e. Then, these metal films are patterned. Thus, a bit line 25 a isformed in the memory cell region A, and wirings 25 b, 25 c, 25 d areformed in the peripheral circuit region B. It should be noted that theAl—Cu film contains Cu by 0.5%, for example. The bit line 25 a and thewirings 25 b, 25 c, 25 d are the first-layer aluminum wiring.

Then, a fourth interlayer insulating film (second insulating film) 26made of SiO₂ and having a thickness of about 2.3 μm is formed on thethird interlayer insulating film 24, the bit line 25 a, and the wirings25 b to 25 d by the plasma CVD method using the TEOS gas.

Then, in order to planarize the fourth interlayer insulating film 26,the step of polishing an upper surface of the fourth interlayerinsulating film 26 by virtue of the CMP method is employed. A polisheddepth of the film 26 is set to about 1.2 μm. Then, the reforming of thefourth interlayer insulating film 26 is carried out by the N₂O plasmaprocess. The conditions of this N₂O plasma process are set to the sameconditions as the N₂O plasma process applied to the second interlayerinsulating film 21.

Then, as shown in FIG. 9, a re-deposited interlayer insulating film 27of about 300 nm thickness is formed on the fourth interlayer insulatingfilm 26 by the plasma CVD method using TEOS. Then, the reforming of there-deposited interlayer insulating film 27 is carried out by the N₂Oplasma process. The conditions of this N₂O plasma process are set to thesame conditions as the N₂O plasma process applied to the secondinterlayer insulating film 21.

Next, steps for forming the structure shown in FIG. 10 will be explainedhereunder.

First, the re-deposited interlayer insulating film 27 and the fourthinterlayer insulating film 26 are patterned by the photolithographymethod. Thus, a via hole 26 a that reaches the first-layer aluminumlayer, the wiring 25 c in the peripheral circuit region B for example,is formed.

Then, a Ti film of 20 nm thickness and a TiN film of 50 nm thickness areformed sequentially on an inner surface of the via hole 26 a and anupper surface of the re-deposited interlayer insulating film 27 by thesputtering. These films are used as a glue layer 29 a. Then, a tungstenfilm 29 b is formed on the glue layer 29 a at the growth temperature of370° C. by using a WF₆ (tungsten hexafluoride) gas, a SiH₄ (silane) gas,and H₂ (hydrogen).

Then, the tungsten film 29 b is removed by the etching-back to leaveonly in the via hole 26 a. At this time, the glue layer 29 a is notremoved. Here, the tungsten film 29 b that is left in the via hole 26 ais used as a conductive plug 28 c.

Then, an Al—Cu film 29 c of 600 nm thickness and a TiN film 29 d of 150nm thickness are formed on the glue layer 29 a and the conductive plug28 c. Here, the Al—Cu film 29 c contains Cu by 3%.

Then, a multi-layered metal film consisting of the glue layer 29 a, theAl—Cu film 29 c, and the TiN film 29 d is patterned. Thus, a metalpattern 31 for covering an area over a plurality of ferroelectriccapacitors 20 is formed in the memory cell region A, and a metal wiring30 is formed in the peripheral circuit region B. Then, the siliconsubstrate 1 is fixed onto the suscepter that is maintained at 350° C.,then the metal pattern 31 is annealed for 30 minute in the oxygenatmosphere at 2 Torr, and then is annealed at 350° C. for 90 minute inthe reduced-pressure atmosphere from which the oxygen is excluded, e.g.,the atmosphere of 1 mTorr or less.

The metal pattern 31 is arranged to cover the ferroelectric capacitors20 sufficiently, and the occupied area of this pattern varies inresponse to the area of the memory cell region A. Here, a cellefficiency is defined as S₁/S₂×100%, where S₁ being an area of thememory cell and S₂ being chip area. When the cell efficiency is 30%, thearea of the metal pattern 31 is set to 30% or more.

According to this, the metal pattern 31 is always arranged to cover theentirety of the memory cell region A. Therefore, a rate of the area ofthe metal pattern 31 to the chip area takes the numerical value higherthan the cell efficiency. This is the case for a second embodimentdescribed later. The stress of the multi-layered metal film thatconsists of the Ti film, the TiN film, the Al—Cu film, and the TiN filmconstituting the metal pattern 31 and the metal wiring 30 exhibits theweak tensile stress of 1×10⁸ dyne/cm² immediately after the formation ofthe multi-layered metal film. However, after such multi-layered metalfilm is annealed in vacuum, the tensile stress is changed into 6×10⁹dyne/cm² to 1×10⁹ dyne/cm² and shows the stronger stress in the tensiledirection than that obtained immediately after the film formation. Sincechange in the stress gives the preferable stress to the underlyingferroelectric capacitors 20, the ferroelectric characteristic of theferroelectric capacitors 20 can be improved.

The TiN film constituting the glue layer 29 a and the TiN film 29 d hasthe compressive stress at the initial stage of the film formation, andthe Al—Cu film 29 c has the tensile stress. Thus, the overallmulti-layered metal film exhibits slight tensile stress.

In this case, a specific resistance of the multi-layered metal film isincreased by 5 to 10% by the annealing.

In the above example, the metal pattern 31 and the metal wiring 30 areformed by patterning the multi-layered metal film, and then themulti-layered metal film is annealed. However, if the multi-layeredmetal film is annealed under the above conditions immediately afterformation of the multi-layered metal film and then the metal pattern 31and the metal wiring 30 are formed by patterning the multi-layered metalfilm, the same stress effect is caused finally in the metal pattern 31and the metal wiring 30. In other words, unless the process of spoilingthe stress in the multi-layered metal film constituting the metalpattern 31 and the metal wiring 30 is executed, the same effect can beexpected by annealing the multi-layered metal film at any stage. Forexample, such annealing may be executed after a first cover film (thirdinsulating film) 32 to be formed in next step is formed.

A potential of the metal pattern 31 is set to a fixed potential or afloating potential that is electrically isolated.

Then, as shown in FIG. 11, the first cover film 32 made of silicon oxideand having a 100 nm thickness is formed on the metal pattern 31, themetal wiring 30, and the re-deposited interlayer insulating film 27 bythe plasma CVD method using the TEOS gas. Then, the N₂O plasma processis applied to the first cover film 32. The conditions of this N₂O plasmaprocess are set to the same conditions as the N₂O plasma process appliedto the second interlayer insulating film 21.

Then, as shown in FIG. 12, a second cover film 33 made of siliconnitride of a 350 nm thickness is formed on the first cover film 32 bythe CVD method. Then, the first and second cover films 32, 33 arepatterned in the area, which is close to the outermost periphery of thechip area (semiconductor device chip area) of the silicon substrate 1,by the photolithography method. Thus, a hole (not shown) connected to asecond-layer aluminum wiring (not shown) is formed.

Then, as shown in FIG. 13, a polyimide resin 34 is coated on the secondcover film 33 as the measure for the crack generation at the time ofpackaging. Then, bonding openings (not shown) are formed in thepolyimide resin 34. Then, the polyimide resin 34 is cured at thetemperature of 250° C. Accordingly, the FeRAM is completed.

In this case, a planar structure of the semiconductor device shown inFIG. 13 is given in FIG. 14. Here, insulating films except the elementisolation insulating film 2 are omitted in FIG. 14.

In the above embodiment, the metal pattern 31 having the tensile stressis formed in the area that is located on the re-deposited interlayerinsulating film 27, which is formed over the ferroelectric capacitors20, to cover the entirety of the memory cell region A. According tothis, the forces applied to the ferroelectric capacitors 20 from theinterlayer insulating films 27, 26, 24 and the cover films 32, 33 havingthe compressive stress can be relaxed by the metal pattern 31. Inaddition, since the metal pattern 31 does not desorb the moisture unlikethe insulating film, the metal pattern 31 does not deteriorate theferroelectric capacitors 20.

Meanwhile, when yield of FeRAM formed via the step of annealing themulti-layered metal film 29 a, 29 c, 29 d constituting the metal pattern31 in the oxygen atmosphere and yield of FeRAM formed without suchannealing step were examined, results shown in FIG. 15 were obtained.

In FIG. 15, PT1 denotes yield in the quantity of initial production,which was examined by measuring the characteristic of the ferroelectriccapacitor at the initial stage of FeRAM formation. Also, PT2 denotesyield in the quantity of initial production, which was examined bymeasuring the retention and imprint characteristics of the ferroelectriccapacitor after the FeRAM was heated at 200° C. for 4 hours.

Also, in FIG. 15, “O₂ anneal” denotes the FeRAM formed via the step ofannealing the multi-layered metal film constituting the metal pattern 31in the oxygen atmosphere. Also, “SiO₂ provided+O₂ anneal” denotes theFeRAM formed via the step of annealing the metal pattern 31 after theSiO₂ film of 80 nm thickness is formed as the first cover film 32 on themulti-layered metal film. Also, “no anneal” denotes the FeRAM formedwithout the step of annealing the multi-layered metal film constitutingthe metal pattern 31.

According to FIG. 15, in the FeRAMs formed via the step of annealing themulti-layered metal film constituting the metal pattern 31, there was nodifference between the yields PT1 and PT2. The products that are goodimmediately after the manufacture of the FeRAM could still maintain thememory cell characteristics as they are after the annealing executed at200° C. for 4 hours.

In contrast, it was found that, in the FeRAMs formed without the step ofannealing the multi-layered metal film, the yield PT2 is degraded lowerthan the yield PT1 and also the FeRAM is degraded by the annealingexecuted at 20° C. for 4 hours.

Next, when a switching charge Q_(SW) and an accumulated charge saturatedvoltage V90 of the ferroelectric capacitor immediately after three typeFeRAMs employed in FIG. 15 are completed were examined, results shown inFIG. 16 were obtained. In this case, the accumulated charge saturatedvoltage V90 is the voltage at which the accumulated charge becomes 90%of the saturated value.

According to FIG. 16, it is appreciated that the ferroelectric capacitorcharacteristics can be improved by annealing the metal film constitutingthe metal pattern 31.

Then, variation in the stress due to the annealing of the metal film wasexamined. As the examined sample, the Al—Cu film of 500 nm thickness andthe TiN film of 100 nm thickness were formed as the metal film on theSiO₂ film that has a 100 nm thickness and covers the silicon substrate.Then, when the change in stress was examined by annealing the metalfilm, results shown in FIG. 17 were obtained. In this case, as theannealing conditions, the temperature was set to 35° C. in theatmosphere of 2.2 Torr, the annealing time was set to 30 min, 60 min,and 120 min, and one of the oxygen gas and the nitrogen gas was selectedas the gas that is introduced into the annealing atmosphere.

In FIG. 17, an abscissa denotes the conditions of the annealing. Also,in FIG. 17, ♦ denotes the no-annealing state that was not annealed underthe conditions given by the abscissa.

According to FIG. 17, it was found that, if the metal film is annealedin the reduced-pressure atmosphere into which the oxygen or the nitrogenis introduced, the tensile stress of the metal film containing thealuminum film is increased as the annealing time is lengthened. In otherwords, the tensile stress can be controlled by the time and thus theoptimal value can be selected in response to the magnitude of thecompressive stress of the interlayer insulating film.

By the way, in the above embodiment, the metal pattern formed on there-deposited interlayer insulating film 27 to cover the entirety of thememory cell region A is made of the multi-layered metal film containingthe Al—Cu film, but other film except the multi-layered metal film maybe employed. That is, as the metal film constituting the metal pattern31, a film made of any one of aluminum, copper, tungsten, titanium, andtantalum, or a film made of an alloy of any element of them or a mixtureof them may be formed. When the aluminum film is formed, it ispreferable to make its thickness more than 250 nm. As the example inwhich the metal pattern 31 is formed of tungsten, the tungsten film 29 bconstituting the conductive plug 28 c may be left selectively on there-deposited interlayer insulating film 27 in the memory cell region A,then this tungsten film may be used as the metal pattern 31. The copperfilm has the compressive stress of −5×10¹⁰ dyne/cm² in the initial stageof film formation. But such compressive stress is changed into thetensile stress of 5×10¹⁰ dyne/cm² when the copper film is annealed atthe temperature of 370° C., for example, in the inert gas atmosphere.

In this case, the annealing of the metal film constituting the metalpattern 31 may be executed in any one of the oxygen atmosphere, theoxygen containing atmosphere, the inert gas atmosphere, and the inertgas containing atmosphere.

Also, if the metal film is heated in the annealing to exceed the meltingpoint, such metal film does not generate the desired stress. Therefore,the annealing temperature must be set to less than the melting point ofthe metal film.

Second Embodiment

The present invention can be applied to the damascene process. Suchapplication of the present invention will be explained hereunder.

FIG. 18A to FIG. 32 are sectional views showing a manufacturing methodof a semiconductor device according to a second embodiment of thepresent invention in order of step. In this embodiment, a stacked FeRAMwill be explained hereunder. But the present invention is not limited tothis embodiment, and can be applied to the planar FeRAM.

First, steps required until a sectional structure shown in FIG. 18A isformed will be explained hereunder.

As shown in FIG. 18A, an element isolation recess is formed around thetransistor forming region of an n-type silicon (semiconductor) substrate51 by the photolithography method, and then an STI element isolationinsulating film 52 is formed by burying silicon oxide (SiO₂) in therecess. In this case, the insulating film formed by the LOCOS method maybe employed as the element isolation insulating film 52.

Then, a p-well 53 is formed by selectively introducing the p-typeimpurity into the predetermined transistor forming region of the siliconsubstrate 51. Then, a silicon oxide film serving as a gate insulatingfilm 54 is formed by thermally oxidizing a surface of the p-well 53 ofthe silicon substrate 51.

Then, an amorphous silicon or polysilicon film and a tungsten silicidefilm are formed sequentially on the overall upper surface of the siliconsubstrate 51. Then, gate electrodes 56 a, 56 b are left on the gateinsulating film 54 by patterning the silicon film and the tungstensilicide film by virtue of the photolithography method. In this case,these gate electrodes 56 a, 56 b constitute a part of the word line(WL).

Then, the b-type impurity, e.g., phosphorus is ion-implanted into thep-well 53 on both sides of the gate electrodes 56 a, 56 b. Thus, firstto third n-type impurity diffusion-regions 55 a to 55 c are formed asthe source/drain. Then, an insulating film, e.g., a silicon oxide (SiO₂)film is formed on the overall surface of the silicon substrate 51 by theCVD method. Then, insulating sidewalls 57 are left on both side portionsof the gate electrodes 56 a, 56 b by etching back the insulating film.

Then, the n-type impurity is ion-implanted again into the first to thirdn-type impurity diffusion regions 55 a to 55 c while using the gateelectrodes 56 a, 56 b and the sidewalls 57 as a mask. Thus,high-concentration impurity regions are formed in the first to thirdn-type impurity diffusion regions 55 a to 55 c respectively, so that thefirst to third n-type impurity diffusion regions 55 a to 55 c have theLDD (Lightly Doped Drain) structure respectively.

The first and third n-type impurity diffusion regions 55 a, 55 c out ofthe above diffusion regions are connected electrically to the capacitorlower electrodes described later, while the second n-type impuritydiffusion region 55 b is connected electrically to the bit linedescribed later.

According to the above steps, two n-type MOS transistors T₁, T₂ havingthe gate electrodes 56 a, 56 b and the n-type impurity diffusion regions55 a to 55 c are formed on the p-well 53 to have one n-type impuritydiffusion region 55 b commonly.

Then, as a cover insulating film 58 for covering the MOS transistors T₁,T₂, a silicon oxide nitride (SiON) film of about 200 nm thickness isformed on the overall surface of the silicon substrate 51 by the plasmaCVD method. Then, a silicon oxide (SiO₂) film of about 1.0 μm thicknessis formed as an underlying insulating film 59 on the cover insulatingfilm 58 by the plasma CVD method using the TEOS gas.

Then, an upper surface of the underlying insulating film 59 isplanarized by the chemical mechanical polishing (CMP) method. Then, thedensification and the dehydrating process of the underlying insulatingfilm 59 are carried out by annealing such underlying insulating film 59at about 650° C. for about 30 minute in the N₂ atmosphere.

Next, steps required until a structure shown in FIG. 18B is obtainedwill be explained hereunder.

First, the cover insulating film 58 and the underlying insulating film59 are patterned by the photolithography method. Thus, contact holes 59a to 59 c reaching the first to third n-type impurity diffusion regions55 a to 55 c respectively are formed.

Then, a titanium (Ti) film of about 20 nm thickness and a titaniumnitride (TiN) film of about 50 nm thickness are formed as a glue film 60in this order on an upper surface of the underlying insulating film 59and inner surfaces of the contact holes 59 a to 59 c by the sputtermethod. Then, a tungsten (W) film 61 is grown on the glue film 60 tobury completely insides of the contact holes 59 a to 59 c by the CVDmethod using tungsten hexafluoride (WF₆).

Then, as shown in FIG. 18C, the tungsten film 61 and the glue film 60are polished selectively by the CMP method while using the underlyinginsulating film 59 as a polishing stopper film to remove from the uppersurface of the underlying insulating film 59. Thus, the tungsten film 61and the glue film 60 are left in the contact holes 59 a to 59 c as firstconductive plugs 62 a, 62 c and a second conductive plug 62 b.

Next, steps required until a sectional structure shown in FIG. 19A isobtained will be explained hereunder.

First, an Ir film is formed on the overall surface by the sputter methodto have a thickness of about 200 to 400 nm, e.g., 250 nm. Then, a TiNfilm 63 a is formed on the Ir film by the sputter method to have athickness of about 200 to 400 nm, e.g., 200 nm. Then, an SiO₂ film 63 bis formed on the TiN film 63 a by the plasma CVD method using the TEOSto have a thickness of about 800 to 900 nm, e.g., 800 nm. Then, a resistpattern (not shown) is formed on the SiO₂ film 63 b. Then, hard masks 63are formed by patterning the SiO₂ film 63 b and the TiN film 63 a whileusing the resist pattern as an etching mask.

Then, the silicon substrate 51 is put on the lower electrode in theetching chamber (not shown). Then, the bias voltage is applied to thesilicon substrate 51 by applying the bias high-frequency power of 700 Whaving a frequency of 600 kHz to the lower electrode. Then, thehigh-frequency power of 800 W having a frequency of 13.56 MHz is appliedas the antenna power to the coil provided around the chamber. Also, HBr,O₂, and C₄F₈ are introduced in the chamber at flow rates of 10 sccm, 40sccm, and 5 sccm respectively to hold the pressure in the chamber at 0.4Pa, and the substrate temperature is set to 40° C. As a result, the Iretching atmosphere is set in the interior of the chamber. In this case,the reason why C₄F₈ is added to the etching atmosphere as describedabove is to stabilize the etching process.

Since the hard masks 63 have the etching resistance against the aboveetching atmosphere, such hard masks 63 function as the etching mask andthus the underlying Ir film is etched/patterned selectively. As aresult, conductive oxygen barrier films 64 a, 64 c made of the Ir filmare left selectively on the first conductive plugs 62 a, 62 c.

Since the conductive oxygen barrier films 64 a, 64 c are made of the Irfilm that is excellent in the oxygen-penetration preventing capability,such a situation that the underlying first conductive plugs 62 a, 62 care oxidized in various steps executed later to cause the defectivecontact can be prevented.

Next, steps required until a sectional structure shown in FIG. 19B isobtained will be explained hereunder.

First, an SiON film of about 100 nm thickness is formed as an oxidationpreventing insulating film 65 a on the overall surface by the plasma CVDmethod. Then, an SiO₂ film of about 400 nm thickness is formed as aninsulating adhesive film 65 b on the oxidation preventing insulatingfilm 65 a by the plasma CVD method using TEOS.

Then, the polishing is applied from an upper surface of the insulatingadhesive film 65 b by the CMP method until such polishing is stopped ona surface of the TiN film 63 a. Thus, as shown in FIG. 19C, the SiO₂film 63 b is removed and thus the surface of the TiN film 63 a isexposed.

Then, as shown in FIG. 20A, the TiN film 63 a is removed by exposing theexposed TiN film 63 a to the ammonia peroxide aqueous solution.

Then, as shown in FIG. 20B, a resist is coated as a sacrifice film 66 onthe overall surface to have a thickness of about 1000 nm. As suchresist, the resist whose etching rate is almost identical to etchingrates of the oxidation preventing insulating film 65 a and theinsulating adhesive film 65 b is employed. The etched surface is loweredas the flat surface by etching back such sacrifice film 66 by virtue ofthe plasma etching. Then, as shown in FIG. 20C, the flat upper surfaceof the sacrifice film 66 prior to the etching-back is transferred ontothe oxidation preventing insulating film 65 a and the insulatingadhesive film 65 b after the end of the etching-back. Then, theremaining oxidation preventing insulating film 65 a and the remaininginsulating adhesive film 65 b are used as an insulating oxygen barrierfilm 65.

As has already been described, the oxidation preventing insulating film65 a of the insulating oxygen barrier film 65 is made of the SiON filmand has a role of preventing the underlying second conductive plug 62 bfrom being oxidized by various annealing processes.

Next, steps required until a sectional structure shown in FIG. 21A isobtained will be explained hereunder.

First, an Ir film and an IrO₂ film are formed in this order as anIrO₂/Ir film 67 on the overall surface by the sputter method to have athickness of about 200 nm and a thickness of about 30 nm respectively.The lowermost Ir film of the IrO₂/Ir film 67 functions to prevent theoxidation of the underlying first conductive plug 62 a and prevent thedegradation of its contact characteristic.

Then, a PtO film and a Pt film are formed in this order as a Pt/PtO film68 on the IrO₂/Ir film 67 by the sputter method to have a thickness ofabout 30 nm and a thickness of about 50 nm respectively. The Pt film ofthe Pt/PtO film 68 fulfills a role of uniformly aligning the orientationof the ferroelectric film formed thereon later.

Then, the IrO₂/Ir film 67 and the Pt/PtO film 68 are used as a lowerelectrode conductive film 69.

In this case, in order to prevent the peeling-off of the film, forexample, the insulating adhesive film 65 b may be annealed before orafter the lower electrode conductive film 69. As the annealing method,the RTA executed at 750° C. for 60 second in the argon atmosphere, forexample, may be employed.

Then, a PZT film of about 180 nm thickness is formed as a ferroelectricfilm 70 on the lower electrode conductive film 69 by the sputter method.As the film forming method of the ferroelectric film 70, there are theMOD method, the MOCVD method, the sol-gel method, etc. in addition tothe sputter method. Also, as the material of the ferroelectric film 70,other PZT material such as PLCSZT, PLZT, etc., Bi-layered structurecompound material such as SrBi₂Ta₂O₉, SrBi₂(Ta,Nb)₂O₉, etc., and othermetal oxide ferroelectric substance may be employed in addition to PZT.In addition, if the DRAM is to be formed, the high-dielectric materialsuch as (BaSr)TiO₃ (BST), strontium titanate (STO), etc. may be used inplace of the above ferroelectric material.

Then, the ferroelectric film 70 is crystallized by executing theannealing in the oxygen-containing atmosphere. As the annealing process,two-step RTA process having the first step executed at the substratetemperature of 600° C. for a time of 90 second in the mixed gasatmosphere consisting of Ar and O₂, and the second step executed at thesubstrate temperature of 750° C. for a time of 60 second in the oxygenatmosphere, for example, is employed.

Then, an IrO₂ film of 200 nm thickness, for example, is formed as anupper electrode conductive film 71 on the ferroelectric film 70 by thesputter method. Then, in order to recover the damage of theferroelectric film 70 caused at the time of formation of the upperelectrode conductive film 71, the annealing is executed for about 60minute in the furnace (not shown) that is set to 650° C. in the oxygenatmosphere.

Next, steps required until a sectional structure shown in FIG. 21B isobtained will be explained hereunder.

First, a TiN film 95 is formed on the upper electrode conductive film 71by the sputter method, and then a SiO₂ film 96 is formed thereon by theplasma CVD method using the TEOS. Then, hard masks 97 are formed bypatterning the TiN film 95 and the SiO₂ film 96 into a capacitor shapeby virtue of the photolithography method.

Then, the silicon substrate 51 is loaded on the lower electrode in theetching chamber (not shown). Then, the bias voltage is applied to thesilicon substrate 51 by applying the bias high-frequency power of 700 Whaving a frequency of 600 kHz to the lower electrode. Then, thehigh-frequency power of 800 W having a frequency of 13.56 MHz is appliedas the antenna power to the coil provided around the chamber. Also, HBrand O₂ are introduced in the chamber at flow rates of 10 sccm and 40sccm respectively to hold the pressure in the chamber at 0.4 Pa, and thesubstrate temperature is set to 400° C. As a result, the IrO₂ etchingatmosphere is set in the interior of the chamber, and the upperelectrode conductive film 71 made of IrO₂ is etched. Then, if theetching is ended when 10% over-etching of the upper electrode conductivefilm 71 is attained, the upper electrode conductive film 71 is etchedinto the shape of the hard mask 97 to form an upper electrode 71 a. Inthis case, the “10% over-etching” signifies that the upper electrodeconductive film 71 is excessively etched only by 10% of a film thickness200 nm of the upper electrode conductive film 71, i.e., a 20 nmthickness.

Then, the inside of the chamber is changed to the PZT etching atmosphereby changing the etching gas into a gas consisting of 40 sccm Cl₂ and 10sccm Ar while maintaining the bias power and the antenna power as theyare. Then, the ferroelectric film 70 is etched into the shape of thehard mask 97. Then, the etching is stopped on the lower electrodeconductive film 69 by monitoring an end point of the etching by means ofan end point detector. Thus, the ferroelectric film 70 is etched to forma capacitor dielectric film 70 a.

Then, the etching of the lower electrode conductive film 69 is startedafter the etching gas is set once again to the gas consisting of 10 sccmHBr and 40 sccm O₂. Then, the etching is ended when the 10% over-etchingis attained. Thus, the lower electrode conductive film 69 is etched intothe shape of the hard mask 97 to form a lower electrode 69 a.

According to these steps, ferroelectric capacitors Q1, Q2 which areformed by laminating the lower electrode 69 a, the ferroelectric film 70a, and the upper electrode 71 a in this order are formed on theunderlying insulating film 59 via the conductive oxygen barrier films 64a, 64 c and the insulating oxygen barrier film 65. The ferroelectriccapacitors Q1, Q2 are connected electrically to the first n-typeimpurity diffusion region 55 a and the third n-type impurity diffusionregion 55 c via the conductive oxygen barrier films 64 a, 64 c and thefirst conductive plugs 62 a, 62 c respectively.

A part of the ferroelectric capacitors Q1, Q2 is formed on theinsulating oxygen barrier film 65. However, since the uppermost layer ofthe insulating oxygen barrier film 65 is formed by the insulatingadhesive film 65 b made of SiO₂, it can be prevented that the lowerelectrodes 69 a of the ferroelectric capacitors Q1, Q2 are peeled offfrom the insulating oxygen barrier film 65.

Then, in order to recover the damage of the dielectric film 70 a causedby the etching, the recovery annealing is carried out. The recoveryannealing in this case is executed at the substrate temperature of 650°C. for 60 minute in the furnace containing the oxygen, for example.

Even if such recovery annealing is carried out, the oxidation of thesecond conductive plug 62 b can be prevented by the insulating oxygenbarrier film 65 and also the oxidation of the first conductive plugs 62a, 62 c can be prevented by the conductive oxygen barrier films 64 a, 64c. In this case, the hard masks 97 are removed after the ferroelectriccapacitors Q1, Q2 are formed.

Then, as shown in FIG. 22A, an alumina film of about 50 nm thickness isformed as a first capacitor protection insulating film 73 on theferroelectric capacitors Q1, Q2 and the insulating oxygen barrier film65 by the sputter method. This first capacitor protection insulatingfilm 73 protects the ferroelectric capacitors Q1, Q2 from the processdamage, and may be formed of PZT in addition to the alumina.

Then, an SiO₂ film of about 100 nm thickness is formed as a secondcapacitor protection insulating film 72 on the first capacitorprotection insulating film 73 by the plasma CVD method using the TEOS.

Then, as shown in FIG. 22B, a first insulating film 74 made of SiO₂ andhaving a thickness of about 1.5 μm is formed on the second capacitorprotection insulating film 72 by the HDPCVD (High Density Plasma CVD)method using SiH₄. According to such HDPCVD method, because the biasvoltage is applied to the silicon substrate 51, the first insulatingfilm 74 with the good burying property can be formed between theferroelectric capacitors Q1, Q2 having a high aspect ratio without thegeneration of voids.

However, since SiH₄ having the hydrogen with the reducing property isused as the reaction gas in the above HDPCVD method, it is possible thatthe dielectric film 70 a is degraded by the hydrogen. For this reason,it is preferable that the hydrogen in the atmosphere should be oxidizedas much as possible by supplying O₂ 5 times or more of SiH₄ at a flowrate to prevent the degradation of the dielectric film 70 a due to thehydrogen as much as possible.

Also, although the reason is not known apparently, if the secondcapacitor protection insulating film 72 is formed by the plasma CVDmethod using the TEOS, the degradation of the ferroelectric capacitorsQ1, Q2 can be prevented more surely than the case where the firstcapacitor protection insulating film 73 is employed as a single layer.

Then, as shown in FIG. 23A, an SiO₂ film of about 500 nm thickness isformed as a CMP sacrifice film 75 on the first insulating film 74 by theplasma CVD method using the TEOS.

Then, as shown in FIG. 23B, a surface of the first insulating film 74 isplanarized by polishing the sacrifice film 75 by means of the CMP. Thus,a thickness of the first insulating film 74 on the upper electrode 71 ais set to about 500 mm.

Then, as shown in FIG. 24A, a BN film (dielectric constant: about 2) ofabout 200 nm thickness is formed as a first low dielectric constantinsulating film 76 on the planarized first insulating film 74.

The first low dielectric constant insulating film 76 is formed on theplanarized first insulating film 74 without the level difference by thewiring. Thus, the method that is capable of providing the good buryingproperty, e.g., the HDPCVD method in which the substrate bias voltage isapplied, is not needed as the film forming method. Therefore, the aboveBN film can be formed in the condition that the bias voltage is notapplied the silicon substrate 51 (non bias), e.g., such film can beformed by the non-bias plasma CVD method using B₂H₆ and N₂ as thereaction gas.

Because of non-bias, the hydrogen in the film forming gas is neverpulled into the silicon substrate 51 by the bias voltage. Thus, such asituation can be prevented that the ferroelectric capacitors Q1, Q2 aredeteriorated by the hydrogen.

Here, as the low dielectric constant insulating film 76, the film formedby the SOL-GEL method may be used in addition to the BN film. In thiscase, it is preferable that a block film (not shown) for blocking thedegas from the first low dielectric constant insulating film 76 shouldbe formed on the first insulating film 74 and then the first lowdielectric constant insulating film 76 should be formed on this blockfilm. As such block film, an SiN film, an SiO₂ film, an SiC film, aTiO_(x) film, etc. formed by the Cat-CVD (Catalytic Chemical VaporDeposition) method, for example, may be listed.

Then, an SiO₂ film of 100 nm thickness is formed as a first cap film 77on the first low dielectric constant insulating film 76 by the plasmaCVD method using the TEOS. This first cap film 77 performs a role ofpreventing the upward diffusion of the degas from the first lowdielectric constant insulating film 76. In this case, various filmsformed by the above Cat-CVD method may be used as the first cap film 77.Then, because this first cap film 77 is also formed on the flat surface,there is no necessity that such film must be formed by the HDPCVDmethod.

According to these steps, a first interlayer insulating film 118consisting of the insulating films 72 to 74, 76, 77 is formed to coverthe ferroelectric capacitors Q1, Q2.

Next, steps required until a sectional structure shown in FIG. 24B isobtained will be explained hereunder.

First, a photoresist is coated on the first cap film 77, and then afirst resist pattern 78 having resist openings 78 a like the hole shapeis formed by exposing/developing the photoresist. Then, the first capfilm 77, the first low dielectric constant insulating film 76, the firstinsulating film 74, and the second capacitor protection insulating film72 are etched while using the first resist pattern 78 as the etchingmask, and thus first holes 72 a, 74 a, 76 a, 77 a are formed inrespective films.

As the etching gas in this case, a mixed gas consisting of CF₄, C₄F₈, O₂and Ar, for example, is used.

Since the selective etching ratio of alumina to SiO₂ in this etching isgiven as (alumina):(SiO₂)=1:about 2 to 3, the first capacitor protectioninsulating film 73 made of alumina fulfills the role of the etchingstopper film in this etching.

After this etching is ended, the first resist pattern 78 is removed bythe ashing using the oxygen plasma.

Next, steps required until a sectional structure shown in FIG. 25A isobtained will be explained hereunder.

First, the photoresist is coated on the overall surface. Then, a secondresist pattern 79 having a first resist opening 79 a having a hole shapeand second resist openings 79 b each having a wiring shape is formed byexposing/developing the photoresist. Then, the first cap film 77, thefirst low dielectric constant insulating film 76, the first insulatingfilm 74, and the second capacitor protection insulating film 72positioned under the first resist opening 79 a are etched while usingthe second resist pattern 79 as an etching mask. Thus, third holes 76 c,77 c and second holes 74 b, 72 b are formed in respective films. As theetching gas in this etching, a mixed gas consisting of CF₄, C₄F₈, O₂,and Ar, for example, is used.

Here, these holes can be formed in the foregoing etching steps (FIG.24B). In this case, a summed depth of these holes is deeper than a totaldepth of respective holes ˜72 a, 74 a, 76 a, 77 a on the ferroelectriccapacitors Q1, Q2. Therefore, it is possible that the first capacitorprotection insulating film 73 on the ferroelectric capacitors Q1, Q2 isetched and the ferroelectric capacitors Q1, Q2 are exposed to theetching atmosphere for a long time and are damaged.

Here, reference is made to FIG. 25A again. In the above etching, thefirst cap film 77 and the first low dielectric constant insulating film76 positioned under the second resist openings 79 b are etched, andsecond holes 76 b, 77 b are formed in respective films. Each of firstwiring recesses 80 consists of the second holes 76 b, 77 b.

In this case, the first capacitor protection insulating film 73 underthe first holes 72 a is etched in this etching, and the first holes 73 aare formed therein. Thus, first contact holes 81 each consisting of theholes 72 a to 74 a are formed to extend downward from the bottomportions of the first wiring recesses 80, and also the upper electrodes71 a of the ferroelectric capacitors Q1, Q2 are exposed from insides ofthe first contact holes 81.

After these steps are ended, the second resist pattern 79 is removed bythe ashing using the oxygen plasma.

Then, in order to recover the damages that the ferroelectric capacitorsQ1, Q2 receive in the steps until now after the ferroelectric capacitorsQ1, Q2 are formed, the oxygen annealing is executed at 550° C. for 60minute in the oxygen atmosphere. Since the insulating oxygen barrierfilm 65 is formed on the second conductive plug 62 b, the oxidation ofthe second conductive plug 62 b during the oxygen annealing can beprevented.

Next, steps required until a sectional structure shown in FIG. 25B isobtained will be explained hereunder.

First, the photoresist is coated on the overall surface. Then, a thirdresist pattern 82 having a resist opening 82 a of a wiring shape isformed by exposing/developing the photoresist.

Then, the first cap film 77 and the first low dielectric constantinsulating film 76 located under the resist opening 82 a are etchedwhile using the third resist pattern 82 as the etching mask. Thus,fourth holes 76 d, 77 d are formed in respective films and used as asecond wiring recess 83. As the etching gas in this etching, a mixed gasconsisting of CF₄, C₄F₈, O₂, and Ar, for example, is employed.

Also, the first capacitor protection insulating film 73, the insulatingadhesive film 65 b, and the oxidation preventing insulating film 65 aunder the second hole 72 b are etched in this etching. Thus, a secondhole 73 b and first holes 65 d, 65 c are formed in respective films.Then, respective holes 74 b, 72 b, 73 b, 65 d, 65 c are used as a secondcontact hole 84.

In this case, after this step is ended, the third resist pattern 82 isremoved by the ashing using the oxygen plasma.

Next, steps required until a sectional structure shown in FIG. 26A isobtained will be explained hereunder.

First, respective upper surfaces of the upper electrodes 71 a and thesecond conductive plug 62 b are etched by using the Ar plasma by about20 nm to expose the cleaned surface. Then, a TaN film of about 50 nm isformed as a first diffusion preventing film 85, which prevents thediffusion of the copper, on inner surfaces of the first and secondcontact holes 81, 84 and the first and second wiring recesses 80, 83 bythe sputter method.

Then, as shown in FIG. 26B, a Cu seed layer (not shown) is formed on theoverall surface. Then, a first copper film 86 having a thickness, whichcan bury perfectly inner surfaces of the first and second contact holes81, 84 and the first and second wiring recesses 80, 83, is formed by theplating method while supplying the electric power to the Cu seed layer.In such plating method, a plating solution into which the organicsubstance to improve the burying property of the copper is added inaddition to copper sulfate is employed. According to the plating method,since the substrate 51 is not heated, the thermal budget is lowered andthus it can be prevented that the ferroelectric capacitors Q1, Q2 aresubjected to the damage by the heat.

In this case, the first copper film 86 may be formed by the CVD methodinstead of the plating method. In such CVD method, the silicon substrate51 is loaded on a substrate loading table 125 in a chamber 124 shown inFIG. 33, and then a Cl2 gas is introduced from the top of the chamber124. Then, the Cl plasma is generated in the chamber 124 by supplying ahigh-frequency power generated by a high-frequency power supply 128,having a frequency of 13.56 MHz and a power of 3000 W, to a coil 126.Then, the Cl plasma is passed through openings 127 a of a copper film127 that is held at the temperature of about 30° C. According to this,the copper in the copper plate 127 is exposed to the Cl plasma togenerate a copper chloride of Cu_(x)Cl_(y), and such copper chloride isadhered onto the silicon substrate 51. Since the silicon substrate 51 isheld at about 200° C. that is lower than the Cl plasma, the Cl inCu_(x)Cl_(y) is desorbed because of temperature difference between thesilicon substrate 51 and the plasma. Thus, only the Cu is deposited ontothe silicon substrate 51 and then the first copper film 86 is formed.

In this manner, if the first copper film 86 is formed by the CVD method,exposure of the first copper film 86 to the atmosphere after itsformation must be avoided to prevent the formation of the natural oxidefilm on a surface of the first copper film 86.

Next, steps required until a sectional structure shown in FIG. 27 isobtained will be explained hereunder.

First, the first copper film 86 and the first diffusion preventing film85 formed over the first cap film 77 are polished by the CMP method toremove. The first copper film 86 and the first diffusion preventing film85 that are left in the first and second wiring recesses 80, 83 and thefirst and second contact holes 81, 84 are used as first and secondcopper wirings 86 a, 86 c and first and second copper plugs 86 b, 86 d.In this case, the first copper wirings 86 a are connected electricallyto the upper electrodes 71 a of the ferroelectric capacitors Q1, Q2 viathe first copper plugs 86 b, and function as the plate line. Also, thesecond copper wiring 86 c is connected electrically to the second n-typeimpurity diffusion region 55 b via the second copper plug 86 d and thesecond conductive plug 62 b, and functions as the bit line.

Such method of forming the copper wiring is called the dual-damasceneprocess.

Then, in order to prevent the upward diffusion of the copper, a seconddiffusion preventing film 87 is formed on the overall surface. As thesecond diffusion preventing film 87, an SiN film having a thickness of70 nm, for example, can be employed. It is preferable that, in order toavoid the damage of the ferroelectric capacitors Q1, Q2, the SiN filmshould be formed by the non-bias plasma CVD method. Otherwise, the BNfilm, the SiC film, and the alumina film may be employed in place of theSiN film. In addition, a conductive film made of Ta, TaN, Ti, TiN, etc.formed by the sputter method may be employed as the second diffusionpreventing film 87 in place of such insulating film. If such conductivefilm is employed, the step of patterning the conductive film intorespective shapes of the copper wirings 86 a, 86 c is executed after theformation of such conductive film, to prevent the electrical connectionbetween the copper wirings 86 a, 86 c.

Next, steps required until a sectional structure shown in FIG. 28 isobtained will be explained hereunder.

First, an SiO₂ film of about 500 nm thickness is formed as a secondinsulating film 88 on the second diffusion preventing film 87 by theplasma CVD method using the TEOS. Then, a BN film of about 200 nmthickness is formed as a second low dielectric constant insulating film89 on the second insulating film 88 by the non-bias plasma CVD methodusing B₂H₆ and N₂ as a reaction gas. Then, an SiO₂ film of 100 nmthickness is formed as a second cap film 90 on the second low dielectricconstant insulating film 89 by the plasma CVD method using the TEOS. Thesecond cap film 90 functions to prevent the upward diffusion of the gasthat is desorbed from the second low dielectric constant insulating film89.

According to the steps executed up to now, a second interlayerinsulating film 119 consisting of respective insulating films 87 to 90is formed.

Next, steps required until a sectional structure shown in FIG. 29 isobtained will be explained hereunder.

First, a resist (not shown) is coated on the second cap film 90. Then, aresist pattern (not shown) having an opening of a metal pattern shape isformed by exposing/developing the resist. Then, the second cap film 90and the second low dielectric constant insulating film 89 are etched byusing the resist pattern as the etching mask. Thus, first holes 89 a, 90a constituting a metal pattern recess 92 are formed in these films. Themetal pattern recess 92 is formed over the ferroelectric capacitors Q1,Q2 and their peripheral areas to cover the cell region containing theferroelectric capacitors Q1, Q2.

Then, as shown in FIG. 30, a TaN film of about 30 nm thickness is formedas a third diffusion preventing film 130 in the metal pattern recess 92.Then, a second copper film 131 is formed on the third diffusionpreventing film 130 by the sputter method, the plating method, or theCVD method. A thickness of the second copper film 131 is set to buryperfectly the metal pattern recess 92.

Then, as shown in FIG. 31, the third diffusion preventing film 130 andthe second copper film 131 are polished by the CMP method. Thus, thethird diffusion preventing film 130 and the second copper film 131 areremoved from an upper surface of the second cap film 90, and also areleft in the metal pattern recess 92 to constitute a metal pattern 132.

This metal pattern 132 is formed wider than the cell region to coversufficiently the ferroelectric capacitors Q1, Q2. Also, its potential isnot limited, and either a fixed potential or a floating potential thatis isolated electrically may be employed.

Then, the silicon substrate 51 is fixed onto the suscepter that is heldat 370° C. Then, the metal pattern 132 is annealed for 30 minute in thereduced-pressure atmosphere of the inert gas, e.g., in the N₂ atmosphereat the pressure of 2 Torr.

The second copper film 131 in the metal pattern 132 has the compressivestress of −5×10¹⁰ dyne/cm² prior to this annealing, but such stress ischanged into the tensile stress of 5×10¹⁰ dyne/cm² after this annealing.Since such change in the stress provides the preferable stress to theunderlying ferroelectric capacitors Q1, Q2, ferroelectric substancecharacteristic of the ferroelectric capacitors Q1, Q2 can be improved.

In the above, the metal film consisting of the third diffusionpreventing film 130 and the second copper film 131 is polished by theCMP method, and then the metal pattern 132 is annealed. But the sequenceof the formation of the metal pattern 132 and the annealing thereof isnot limited. For example, it is expected that, even if the annealing isapplied to the metal film under the above conditions before the CMP, thesame stress effect as the above can be produced in the metal pattern132. In addition, the annealing may be carried out after a fourthdiffusion preventing film 100 described later is formed on the metalpattern 132.

In that annealing, if the metal film is heated in excess of the meltingpoint, the metal film is melted and the metal film does not generate thedesired stress. Therefore, the annealing temperature must be set to themelting point or less of the metal film.

In addition, execution of this annealing is not limited in thereduced-pressure atmosphere of the inert gas, and such annealing may beexecuted in the oxygen atmosphere, the oxygen-containing atmosphere, andthe inert gas-containing atmosphere.

Next, steps required until a sectional structure shown in FIG. 32 isobtained will be explained hereunder.

First, an alumina film or a Ta film of about 70 nm thickness is formedas the fourth diffusion preventing film 100 on the metal pattern 132 andthe second cap film 90 by the sputter method. Since the fourth diffusionpreventing film 100 is formed by the sputter method, the film formingatmosphere does not become the reducing atmosphere. Thus, it can beprevented that the ferroelectric capacitors Q1, Q2 are degraded by thereducing atmosphere.

In this case, if the Ta film is used as the fourth diffusion preventingfilm 100, the Ta film is patterned into the shape of the metal pattern132 after the formation of the Ta film, to prevent the situation thatthe metal pattern 132 is connected electrically to the wiring (notshown) formed in the same layer as the metal pattern 132.

Then, an SiO₂ film of about 100 nm thickness is formed as a thirdinsulating film 101 on the fourth diffusion preventing film 100 by theplasma CVD method using the TEOS. Then, a BN film of about 200 nmthickness is formed as a third low dielectric constant insulating film102 on the third insulating film 101. Then, an SiO₂ film of about 100 nmthickness is formed as a third cap film 103 on the third low dielectricconstant insulating film 102 by the plasma CVD method using the TEOS.

Then, a third copper plug 104 and a third copper wiring 105 are buriedin the fourth diffusion preventing film 100, the third insulating film101, the third low dielectric constant insulating film 102, and thethird cap film 103 by using the dual-damascene process. Both the thirdcopper plug 104 and the third copper wiring 105 have a double-layeredstructure of the TiN film and the copper film, and are connectedelectrically to the underlying metal pattern 132.

Here, the metal pattern 132 is set as a floating potential, there is nonecessity to connect the third copper plug 104 to the metal pattern 132.In this case, a hole may be formed to reach the metal pattern 132, andthen the third copper plug 104 reaching the first copper wiring 86 a maybe formed not to contact to an inner surface of the hole but to passthrough an inside of the hole. If doing this, the hole into which thethird copper plug 104 is to be buried is formed in respective insulatingfilms 87 to 90.

Then, an alumina film or a Ta film of about 70 nm thickness is formed asa fifth diffusion preventing film 106 on the third copper wiring 105 andthe third cap film 103 by the sputter method. If the Ta film is used asthe fifth diffusion preventing film 106, such Ta film is patterned intothe shape of the third copper wiring 105 after the formation.

Then, an SiO₂ film of about 500 nm thickness is formed as a fourthinsulating film 107 on the fifth diffusion preventing film 106 by theplasma CVD method using the TEOS. Then, a fourth low dielectric constantinsulating film 108 made of the BN film, or the like is formed on thefourth insulating film 107 to have a thickness of about 200 nm. Then, anSiO₂ film is formed as a fourth cap film 109 by the plasma CVD methodusing the TEOS.

Then, fourth copper wirings 110 are buried in the fifth diffusionpreventing film 106, the fourth insulating film 107, the fourth lowdielectric constant insulating film 108, and the fourth cap film 109 bythe dual-damascene process. The fourth copper wiring 110 has adouble-layered structure consisting of the TiN film and the copper film,and is connected electrically to the third copper wiring 105 via thecopper plug (not shown).

Then, an alumina film or a Ta film of about 70 nm thickness is formed asa sixth diffusion preventing film 111 on the fourth copper wiring 110and the fourth cap film 109 by the sputter method. If the Ta film isused as the sixth diffusion preventing film 111, such Ta film ispatterned into the shape of the fourth copper wiring 110 after the Tafilm is formed. Then, an SiO₂ film of about 500 nm thickness is formedas a fifth insulating film 112 on the sixth diffusion preventing film111 by the plasma CVD method using the TEOS. Then, a hole is formed inthe fifth insulating film 112 and the sixth diffusion preventing film111 by the photolithography method, and then a third conductive plug 113is formed in the hole. The third conductive plug 113 has a laminatedstructure in which a TaN film, a TiN film, and a tungsten film arelaminated from the bottom, for example.

Then, a multi-layered metal film is formed on the third conductive plug113 and the fifth insulating film 112. As the multi-layered metal film,a Ti film of 60 nm thickness, a TiN film of 30 nm thickness, an Al—Cufilm of 400 nm thickness, a Ti film of 5 nm thickness, and a TiN film of70 nm thickness, for example, are formed sequentially by the sputtermethod. Then, a final metal wiring 115 is obtained by patterning themulti-layered metal film by virtue of the photolithography method.

Then, an SiO₂ film of about 1.5 μm is formed as a sixth insulating film114, which covers the final metal wiring 115, by the plasma CVD methodusing the TEOS.

Finally, an SiN film is formed as a surface protection film 116, whichprotects a device surface, to have a thickness of about 500 nm. It ispreferable that the SiN film should be formed by the non-bias plasma CVDmethod, for the purpose of not damaging the ferroelectric capacitors Q1,Q2.

According to the above embodiment, the metal pattern recess 92 isprovided in the second interlayer insulating film 119, and then themetal pattern 132 having the tensile stress is formed therein.Therefore, the compressive stress generated in the second insulatingfilm 88, etc. in the second interlayer insulating film 119 can berelaxed by the metal pattern. As a result, the net stress that isapplied to the ferroelectric capacitors Q1, Q2 can be reduced and thusthe ferroelectric characteristic of the ferroelectric capacitors Q1, Q2can be improved.

In the above, the second interlayer insulating film 119 is composed of aplurality of insulating films 88 to 90. But the second interlayerinsulating film 119 may be formed by a single-layer insulating film.

In addition, in the above, the metal pattern is constructed by themulti-layered metal film consisting of the third diffusion preventingfilm 130 and the second copper film 131, but such metal pattern may beconstructed by other film except the multi-layered metal film. That is,any film made of aluminum, titanium, copper, tantalum, tungsten, or afilm made of any alloy of their elements or their mixture.

As described above, according to the semiconductor device according tothe present invention, the metal pattern having the stress in theopposite direction to the second insulating film is provided. Therefore,the stress applied from the second insulating film to the capacitor canbe relaxed by the stress of the metal pattern and thus the ferroelectriccharacteristic of the capacitor can be improved. In addition, since themetal pattern never desorbs the moisture unlike the insulating film, thecapacitor is never deteriorated by the moisture.

Also, according to the semiconductor device manufacturing methodaccording to the present invention, the stress of the metal film ischanged by heating the metal film at the temperature of the meltingpoint or less before or after the formation of the metal pattern.Therefore, the stress of the second insulating film can be relaxed bythe metal film and thus the ferroelectric characteristic of thecapacitor can be improved.

1-2. (canceled)
 3. A semiconductor device comprising: a first insulatingfilm formed over a semiconductor substrate; a capacitor formed on thefirst insulating film and having a lower electrode, a dielectric film,and an upper electrode; a second insulating film formed over thecapacitor and the first insulating film; a recess formed in the secondinsulating film over the capacitor and a periphery thereof; and a metalpattern formed in the recess and having a stress in an oppositedirection to a stress of the second insulating film. 4-9. (canceled) 10.A manufacturing method of semiconductor device comprising: forming afirst insulating film over a semiconductor substrate; formingcapacitors, each having a lower electrode, a dielectric film, and anupper electrode, on the first insulating film in a cell region; forminga second insulating film over the capacitors and the first insulatingfilm; forming a metal film on the second insulating film; forming ametal pattern, which covers the cell region, by patterning the metalfilm; and heating the metal film at a melting point or less of the metalfilm before or after the formation of the metal pattern, to change astress of the metal film.
 11. A method according to claim 10 furthercomprising: forming a metal wiring in a region, which is away from themetal pattern, by patterning the metal film.
 12. A method according toclaim 10, wherein the second insulating film is a film that is formed byusing a reaction gas containing TEOS.
 13. A manufacturing method ofsemiconductor device comprising: forming a first insulating film over asemiconductor substrate; forming capacitors, each having a lowerelectrode, a dielectric film, and an upper electrode, on the firstinsulating film in a cell region; forming a second insulating film overthe capacitor and the first insulating film; forming a recess, whichcovers the cell region, in the second insulating film; forming a metalfilm, which has a thickness of burying the recess, in the recess and onan upper surface of the second insulating film; removing the metal filmfrom the upper surface of the second insulating film and also leavingthe metal film in the recess as a metal pattern; and heating the metalfilm at a melting point or less of the metal film before or after theformation of the metal pattern, to change a stress of the metal film.14. A method according to claim 13, wherein the second insulating filmis formed of a laminated film consisting of a plurality of insulatingfilms, and at least one layer of the laminated film is a film that isformed by using a reaction gas containing TEOS.
 15. A method accordingto claim 10, wherein heating of the metal film is executed in areduced-pressure atmosphere.
 16. A method according to claim 10, whereinheating of the metal film is executed in any one of an oxygenatmosphere, an oxygen containing atmosphere, an inert gas atmosphere,and an inert gas containing atmosphere.
 17. A method according to claim10 further comprising: forming a third insulating film on the metal filmbefore heating the metal film.
 18. A method according to claim 10,wherein formation of the metal pattern is formation of a film that ismade of any one of material selected from the group consisting ofaluminum, titanium, copper, tantalum, and tungsten, or made of materialcontaining any one selected from the group consisting of aluminum,titanium, copper, tantalum, and tungsten.
 19. A method according toclaim 10, wherein the stress of the metal film is changed into a stress,which is opposite to a stress of the second insulating film, by heatingthe metal film.
 20. A method according to claim 19, wherein the stressof the metal film is changed into a tensile stress by heating the metalfilm.
 21. A method according to claim 10, wherein the second insulatingfilm has a compressive stress.
 22. A method according to claim 10,wherein the metal film is formed to have a single-layer structure or amulti-layered structure.